Sc2C2@C80 rather than Sc2@C82: templated formation of unexpected C2v(5)-C80 and temperature-dependent dynamic motion of internal Sc2C2 cluster

Unambiguous X-ray crystallographic results of the carbene adduct of Sc(2)C(82) reveal a new carbide cluster metallofullerene with the unexpected C(2v)(5)-C(80) cage, that is, Sc(2)C(2)@C(2v)(5)-C(80). More interestingly, DFT calculations and NMR results disclose that the dynamic motion of the internal Sc(2)C(2) cluster depends strongly on temperature. At 293 K, the cluster is fixed inside the cage with two nonequivalent Sc atoms on the mirror plane, thereby leading to C(s) symmetry of the whole molecule. However, when the temperature increases to 413 K, the (13)C and (45)Sc NMR spectra show that the cluster rotates rapidly inside the C(2v)(5)-C(80) cage, featuring two equivalent Sc atoms and weaker metal-cage interactions.     

Functionalization of a simple dithienylethene via palladium-catalyzed regioselective direct arylation

The direct arylation on the thienyl groups of a diarylethene with various aryl iodides efficiently provided arylated dithienylethenes under palladium catalysis. Unsymmetrically substituted dithienylethenes were also synthesized by this protocol. This procedure allows a rapid access to a variety of aryl-substituted dithienylethenes from a single substrate of a simple dithienylethene.     

Distribution of phospholipid molecular species in autogenous access grafts for hemodialysis analyzed using imaging mass spectrometry

Arteriovenous fistulae (AVF) using vein grafts are frequently used for vascular access in hemodialysis. When superficial veins are used as autogenous access grafts for hemodialysis, atherosclerotic-like tissue degeneration often causes stenosis and obstruction. Although the differences between the pathology of degeneration in AVF and atherosclerosis (i.e., peripheral artery occlusive disease (PAD)) are known, their underlying molecular mechanisms are not. We determined the characteristic abnormal lipid metabolism of AVF. Oil red O staining clearly showed the accumulation of lipid molecules in AVF and PAD tissues. We found that the staining pattern was different between AVF and PAD tissues. The media and adventitia of AVF and the intima and media of PAD were intensely stained. Quantitative lipid analysis revealed that the amount of PL was significantly increased in AVF and PAD. Next, we performed matrix-assisted laser desorption/ionization imaging mass spectroscopy and determined the characteristic distribution of lysophosphatidylcholine (LPC) and phosphatidylcholine (PC) in AVF. The distribution patterns of LPC (1-acyl 16:0) and PC (diacyl 16:0/20:4) were consistent with the Oil red O staining images, suggesting that metabolisms related to LPC (1-acyl 16:0) and PC (diacyl 16:0/20:4) are altered in AVF.     

On simulation of tempered stable random variates

Various simulation methods for tempered stable random variates with stability index greater than one are investigated with a view towards practical implementation, in particular cases of very small scale parameter, which correspond to increments of a tempered stable Lévy process with a very short stepsize. Methods under consideration are based on acceptance-rejection sampling, a Gaussian approximation of a small jump component, and infinite shot noise series representations. Numerical results are presented to discuss advantages, limitations and trade-off issues between approximation error and required computing effort. With a given computing budget, an approximative acceptance-rejection sampling technique Baeumer and Meerschaert (2009) [11] is both most efficient and handiest in the case of very small scale parameter and moreover, any desired level of accuracy may be attained with a small amount of additional computing effort.     

A general method for construction of (<Emphasis Type="Italic">t</Emphasis>, <Emphasis Type="Italic">n</Emphasis>)-threshold visual secret sharing schemes for color images

This paper is concerned with the construction of basis matrices of visual secret sharing schemes for color images under the (t, n)-threshold access structure, where n ≥ t ≥ 2 are arbitrary integers. We treat colors as elements of a bounded semilattice and regard stacking two colors as the join of the two corresponding elements. We generate n shares from a secret image with K colors by using K matrices called basis matrices. The basis matrices considered in this paper belong to a class of matrices each element of which is represented by a homogeneous polynomial of degree n. We first clarify a condition such that the K matrices corresponding to K homogeneous polynomials become basis matrices. Next, we give an algebraic scheme for the construction of basis matrices. It is shown that under the (t, n)-threshold access structure we can obtain K basis matrices from appropriately chosen K − 1 homogeneous polynomials of degree n by using simple algebraic operations. In particular, we give basis matrices that are unknown so far for the cases of t = 2, 3 and n − 1.     

Water-dispersible ultrathin Au nanowires prepared using a lamellar template of a long-chain amidoamine derivative

Straight ultrathin Au nanowires (NWs) with diameters less than 2 nm were synthesized using the lamellar structure of C18AA in an organogel and its selective adsorption for specific gold surfaces. In addition, the potential to form a bilayer structure with interdigitated hydrocarbon chains enabled the production of water-dispersible Au NWs without morphological change.     

Formation and dielectric properties of anodic oxide films on Zr–Al alloys

Zr–Al alloys containing up to 26 at.% aluminum, prepared by magnetron sputtering, have been anodized in 0.1 mol dm⁻³ ammonium pentaborate electrolyte, and the structure and dielectric properties of the resultant anodic oxide films have been examined by grazing incidence X-ray diffraction, transmission electron microscopy, Rutherford backscattering spectroscopy, and AC impedance spectroscopy. The anodic oxide film formed on zirconium consists of monoclinic and tetragonal ZrO₂ with the former being a major phase. Two-layered anodic oxide films, comprising an outer thin amorphous layer and an inner main layer of crystalline tetragonal ZrO₂ phase, are formed on the Zr–Al alloys containing 5 to 16 at.% aluminum. Further increase in the aluminum content to 26 at.% results in the formation of amorphous oxide layer throughout the thickness. The anodic oxide films become thin with increasing aluminum content, while the relative permittivity of anodic oxide shows a maximum at the aluminum content of 11 at.%. Due to major contribution of permittivity enhancement, the maximum capacitance of the anodic oxide films is obtained on the Zr–11 at.% Al alloy, being 1.7 times than on zirconium at the formation voltage of 100 V.     

The role of intermolecular hydrogen bond on dielectric properties in hydrogen-bonded material 5-bromo-9-hydroxyphenalenone: theoretical investigation

Dielectric properties of the hydrogen-bonded material, 5-bromo-9-hydroxyphenalenone (C(13)H(7)O(2)Br; BrHPLN), are investigated theoretically by means of electronic structure calculations and Monte Carlo simulations. The density functional calculations of BrHPLN crystals have revealed that the polarization per one molecule can be about 1.7 times larger than that of the isolated monomer. It is also found that there exists significant electron density (0.01 e bohr(-3)) in an intermolecular C-H···O region, which, together with the interatomic distances of 2.39 ? for H···O and 3.34 ? for C···O, suggests the existence of intermolecular weak hydrogen bonding that may enhance the molecular polarization. The induced polarization effects in various intermolecular configurations are evaluated with the Fragment Molecular Orbital method. In addition to the π-π stacking interactions, two types of "in plane" intermolecular weak hydrogen-bonding configurations are found to affect the molecular dipole moment most significantly. These effects are efficiently included in a Monte Carlo simulation method in terms of "dipole corrections" as functions of both the intermolecular arrangements and the intramolecular proton configurations. The application to the dielectric phase transition of a BrHPLN crystal shows that the dipole corrections almost double the transition temperature, toward better agreement with experiments, and qualitatively affect the temperature dependence of the dielectric constant. Discussions are given to support that the results will remain adequate and consistent even after explicit inclusion of the quantum tunneling effects.